Sulfide oxidation process for production of molybdenum oxides from molybdenite

ABSTRACT

A looping method for production of MoO 2 , the method including reacting molybdenite feed with a substantially stoichiometric mixture comprising MoO 3  and oxygen in a first furnace to produce MoO 2  and SO 2 , removing a first portion of the MoO 2  from the first furnace, transferring a second portion of the MoO 2  from the first furnace to a second furnace, reoxidizing of the transferred portion of the MoO 2  in the second furnace to MoO 3 ; and looping the MoO 3  from the second furnace to the first furnace for use as an oxidizing agent.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No. 61/736,114 filed Dec. 12, 2012, which is hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This application is directed to methods for the production of molybdenum oxides from molybdenite, and in particular a looping sulfide oxidation process for the production of molybdenum oxides from molybdenite.

BACKGROUND

Molybdenum (Mo) metal is usually found as deposits of molybdenite (MoS₂) in nature. Traditionally, the metal value is extracted from the sulfidic ore through various pyrometallurgical techniques. The primary application for Mo is in the steel industry, where it is used to produce high strength steel alloys. The Mo used in these applications is supplied to the steel manufacturers either as molybdenum(VI) oxide (molybdenum trioxide, MoO₃) or ferromolybdenum, an iron-molybdenum alloy.

In producing molybdenum trioxide, or so called technical grade oxide, the molybdenite is oxidized in various multiple hearth roasting furnaces. For example, one conversion process, referred to as the Climax conversion process, uses a Nichols Herreshoff or Lurgi design multiple hearth furnace to slowly roast the MoS₂ at temperatures in the range of 530 to 700° C. (L. F. McHugh, P. L. Sallade, Molybdenum Conversion Practice, Metec, Inc.: Winslow N.J., 1977; L. F. McHugh, J. Godshalk, M. Kuzior, Climax Conversion Practice III, The Metallurgical Society of CIM, 1977, 21-24). Over the course of roasting, the molybdenite is first converted to molybdenum(IV) oxide (molybdenum dioxide, MoO₂) and then slowly converted to the trioxide, MoO₃, in the lower hearths. In such a roasting operation, the lower hearths are maintained at lower temperatures to keep the highly volatile MoO₃ from sublimating. The SO₂ produced during conversion, which is highly diluted due to the significant amount of excess air used during roasting, is usually converted to sulfuric acid in a downstream process, which may result in some high pressure steam production.

The molybdenite host ore (unprocessed ore containing molybdenite) is usually concentrated prior to oxidation to upgrade the molybdenite concentration via an oil flotation method. A method has been described wherein the residual flotation oil can be removed in situ during roasting to produce technical grade oxide from the molybdenite without further purification (L. F. McHugh, D. E. Barchers, Roasting of Molybdenite Concentrates Containing Flotation Oils, U.S. Pat. No. 4,523,948, issued Jun. 18, 1985).

In alternative incarnations of MoO₃ production, microwaves have been used to heat molybdenite host ores in the presence of oxygen to convert them to oxides, followed by separation and recovery (P. R. Kruesi, V. H. Frahm, Jr., Process for the Recovery of Molybdenum and Rhenium from their Sulfide Ores, U.S. Pat. No. 4,321,089, issued Mar. 23, 1982). Chlorine can be substituted for oxygen and the metals recovered as chlorides. The conversion can be conducted in a flash roasting set-up wherein the molybdenite is converted to gaseous MoO₃ and any slag-forming constituents are converted to a liquid slag that separates from the molybdenum, wherein the flash roasting is performed at 1600±200° C., and the technical grade oxide is later condensed at significantly lower temperatures (B. J. Sabacky, M. T. Hepworth, Flash Roasting of Molybdenum Sulfide Concentrates in a Slagging Reactor, U.S. Pat. No. 4,555,387, issued Nov. 26, 1985). High pressure oxidation carried out in an autoclave followed by leaching and recovery has also been described (R. W. Balliett, W. Kummer, J. E. Litz, L. F. McHugh, H. H. K. Nauta, P. B. Queneau, R.-C. Wu, Production of Pure Molybdenum Oxide from Low Grade Molybdenite Concentrates, U.S. Pat. No. 6,730,279, issued May 4, 2004).

It is more attractive to the steel industry to use MoO₂ rather than MoO₃ because the lower oxygen content means a higher Mo content, and less reducing agent consumption during the production of molybdenum steels. Additionally, the dioxide is less volatile than the trioxide. The use of MoO₂ also eliminates the need to produce ferromolybdenum. Several authors have attempted to produce the dioxide from molybdenite concentrates using various techniques.

For example, by mixing stoichiometric amounts of powdered or pelletized MoO₃ and MoS₂, MoO₂ can be produced at temperatures of 600 to 700° C. and pressure slightly in excess of atmospheric pressure, while liberating SO₂ (R. Cloppet, Process for the Production of Molybdenum Dioxide, U.S. Pat. No. 3,336,100, issued Aug. 15, 1967). The molybdenum product was then further treated in an SO₂ lean atmosphere to produce the final dioxide product. In a similar process, particulate MoO₂ and MoS₂ (weight ratio 2:1) were roasted at 700 to 800° C. in the presence of enough oxygen to facilitate the conversion of the molybdenite to MoO₂ (B. J. Sabacky, M. T. Hepworth, Molybdenum Dioxide-Molybdenite Roasting, U.S. Pat. No. 4,462,822, issued Jul. 31, 1984). A portion of the dioxide produced was recycled to convert the next charge of molybdenite. Some MoO₃ is produced as a by-product. Pelletized MoO₂ has been produced from MoO₃ using a reducing H₂ atmosphere in a reaction vessel that was able to control the exothermic reduction of the trioxide (H. W. Meyer, J. D. Baker, W. H. Ceckler, Direct Reduction of Molybdenum Oxide to Substantially Metallic Molybdenum, U.S. Pat. No. 4,045,215, issued Aug. 30, 1977). The dioxide was further reduced to metallic Mo, or the dioxide was collected as a final product.

It has also been proposed to convert molybdenite to MoO₂ using water steam (K. Y. Hakobyan, H. Y. Sohn, A. V. Tarasov, P. A. Kovgan, A. K. Hakobyan, V. A. Briovkvine, V. G. Leontiev, and O. I. Tsybine, “New Technology for the Treatment of Molybdenum Sulfide Concentrates,” Sohn International Symposium Advanced Processing of Metals and Materials Vol. 4 to New, Improved and Existing Technologies: Non-Ferrous Materials Extraction and Processing, ed. by F. Kongoli and R. G. Reddy, TMS (The Minerals, Metals & Materials Society), pp. 203-216, 2006; H. Y. Sohn, Process for Treating Sulfide-Bearing Ores, U.S. Pat. No. 4,376,647, issued Mar. 15, 1983; K. Y. Hakobyan, P. A. Kovgan, A. V. Tarasov, A. K. Hakobyan, Eurasian Patent 002417, issued 2002; K. Y. Hakobyan, H. Y. Sohn, A. K. Hakobyan, V. A. Bryukvin, V. G. Leontiev, and O. I. Tsibin, “The Oxidation of Molybdenum Sulfide Concentrate with Water Vapor: Part I. Thermodynamic Aspects,” Mineral Processing and Extractive Metallurgy (TIMM C), 116, 152-154 (2007); K. Y. Hakobyan, H. Y. Sohn, A. K. Hakobyan, V. A. Bryukvin, V. G. Leontiev, and O. I. Tsibin, “The Oxidation of Molybdenum Sulfide Concentrate with Water Vapor: Part II. Macrokinetics and Mechanism,” Mineral Processing and Extractive Metallurgy (TIMM C), 116, 155-158 (2007)). In such a scheme, steam is reacted with the MoS₂ feed to produce the dioxide and an H₂5 off-gas stream. Hydrogen sulfide is a toxic gas and is difficult to handle in downstream processes. A rotating furnace is used to treat molybdenite ores at 900 to 1,000° C. in a countercurrent flow of water vapor in an excess of 6 to 10 times the mass of the molybdenite. Residual sulfur is optimized to minimize the loss of MoO₂ to MoO₃ vapor formation.

Solid MoO₃ has been used in a reaction between MoO₃ and MoS₂ to produce MoO₂ (L. F. McHugh, D. K. Huggins, M. T. Hepworth, J. M. Laferty, Process for the Production of Molybdenum Dioxide, U.S. Pat. No. 4,552,749, issued Nov. 12, 1985). In this process the conversion to dioxide is carried out at temperatures low enough to favor dioxide formation and to produce an SO₂-rich stream (750 to 950° C.). A portion of the MoO₂ product was sent to a flash reactor where it was reoxidized to the trioxide at temperatures sufficient to sublimate the MoO₃ (1,000 to 1,700° C.) and recycled to convert the next charge of molybdenite. In a similar process, the MoO₂ is oxidized in a second step to MoO₃ to recover rhenium from the final product; in this operation the MoO₂ is not the final product (H. Y. Sohn, Process for Treating Sulfide-Bearing Ores, U.S. Pat. No. 4,376,647, issued Mar. 15, 1983).

Solid MoO₃ has been proposed as an oxidant to molybdenite to achieve a high degree of desulfurization; the process required ca. 10% excess MoO₃ to be mixed intimately with the molybdenite in order to achieve a low sulfur content product (L. F. McHugh, R. Balliett, J. A. Mozolic, The Sulfide Ore Looping Oxidation Process: An Alternative to Current Roasting and Smelting Practice, JOM, July 2008, 84-87; L. F. McHugh, Oxidation of metallic materials as part of an extraction, purification, and/or refining process, U.S. Patent Application 2008/0260612 A1, published Oct. 23, 2008). Some of the dioxide was then reoxidized in a flash furnace with oxygen to recycle MoO₃ to the molybdenite charge (similar to as reported in L. F. McHugh, D. K. Huggins, M. T. Hepworth, J. M. Laferty, Process for the Production of Molybdenum Dioxide, U.S. Pat. No. 4,552,749, issued Nov. 12, 1985).

The methods described above all appear to use significant excess oxygen. While these methods produce MoO₂ from molybdenite feeds, it has not been possible to produce a product without concomitantly producing some MoO₃. When it has been used, oxygen has also always been in excess. A method that can produce exclusively MoO₂ is desired.

There accordingly remains a need in the art for methods for the production of MoO₂ from molybdenite. Producing MoO₂ with lower amounts of MoO₃ is considered particularly advantageous. It is further desired that the MoO₂ productions methods allowed control of SO₂ and energy consumption during production.

SUMMARY OF THE INVENTION

The present disclosure provides a pyrometallurgical method for production of molybdenum(IV) oxide, the method including contacting molybdenite feed with oxygen in a furnace including a high temperature zone, wherein an amount of the oxygen is substantially stoichiometric; and reacting the molybdenite feed with the oxygen to produce molybdenum(IV) oxide and sulfur(IV) oxide, wherein complete desulfurization of the molybdenite feed is accomplished in the high temperature zone at a temperature of about 1,000 to about 1,500° C. with a residence time of about 0.1 to about 40 seconds.

The present disclosure also provides a looping method for production of molybdenum(IV) oxide, the method comprising reacting a molybdenite feed with a substantially stoichiometric mixture comprising molybdenum(VI) oxide and oxygen in a first furnace to produce molybdenum(IV) oxide and sulfur(IV) oxide; removing a first portion of the molybdenum(IV) oxide from the first furnace; transferring a second portion of the molybdenum(IV) oxide from the first furnace to a second furnace; reoxidizing the second portion of the molybdenum(IV) oxide in the second furnace to molybdenum(VI) oxide; and looping the molybdenum(VI) oxide from the second furnace to the first furnace for use as an oxidizing agent.

Other embodiments will be apparent from the Drawings, Detailed Description, and Claims below.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:

FIG. 1 shows a predominance phase diagram for the Mo—O—S system at 1,000° C.;

FIG. 2 shows a predominance phase diagram for the Mo—O—S system at 1,250° C.;

FIG. 3 shows a predominance phase diagram for the Mo—O—S system at 1,500° C.;

FIG. 4 shows a thermodynamic equilibrium composition during conventional roasting of 1 mole of Mo S₂;

FIG. 5 shows a thermodynamic equilibrium composition for conversion of 1 mole of Mo S₂ to MoO₂ under stoichiometric O₂;

FIG. 6 shows a thermodynamic equilibrium composition for conversion of 1 mole of MoS₂ to MoO₂ under 5% excess O₂;

FIG. 7 shows a thermodynamic equilibrium composition for conversion of 1 mole of MoS₂ to MoO₂ under conditions utilizing 0.5% excess O₂;

FIG. 8 shows a thermodynamic equilibrium partial pressure of S₂ during oxidation of 1 mole of MoS₂ at various amounts of oxygen;

FIG. 9 shows a thermodynamic equilibrium partial pressure of SO₂ during oxidation of 1 mole of MoS₂ at different amounts of oxygen;

FIG. 10 shows a thermodynamic equilibrium composition for conversion of 1 mole of MoS₂ to MoO₂ under 5% lean O₂;

FIG. 11 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 2.5 moles O₂, 1 mole MoO₃;

FIG. 12 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 2.4 moles O₂, 1.2 moles MoO₃;

FIG. 13 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 2.3 moles O₂, 1.4 moles MoO₃;

FIG. 14 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 2.2 moles O₂, 1.6 moles MoO₃;

FIG. 15 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 2.1 moles O₂, 1.8 moles MoO₃;

FIG. 16 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 2 moles O₂, 2 moles MoO₃;

FIG. 17 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 1.9 moles O₂, 2.2 moles MoO₃;

FIG. 18 shows a thermodynamic equilibrium for combined cycle oxidation of 1 mole of molybdenite; 1.8 moles O₂, 2.4 moles MoO₃;

FIG. 19 illustrates a reoxidation of 1 mole of MoO₂ in excess O₂;

FIG. 20 shows a predominance diagram for the thermodynamic equilibrium in the Mo—S—O system at 500° C.

FIG. 21 shows a predominance diagram for the thermodynamic equilibrium in the Mo—S—O system at 600° C.

FIG. 22 shows a predominance diagram for the thermodynamic equilibrium in the Mo—S—O system at 700° C.

FIG. 23 shows a predominance diagram for the thermodynamic equilibrium in the Mo—S—O system at 900° C.

FIG. 24 shows a thermodynamic equilibrium composition for the oxidation of 1 mole of MoS₂ to MoO₂ using a stoichiometric amount of MoO₃;

FIG. 25 shows a thermodynamic equilibrium composition for the oxidation of 1 mole of MoS₂ in 5% excess MoO₃;

FIG. 26 shows a thermodynamic equilibrium composition for the oxidation of 1 mole of MoS₂ at a 5% shortage of MoO₃;

FIG. 27 displays speciation and phase transition of MoO₃ as a function of temperature;

FIG. 28 is a flow sheet illustrating a MoS₂—MoO₃-Air dual flash looping process;

FIG. 29 is a flow sheet illustrating a MoS₂—MoO₃-Air dual flash looping process with high pressure steam production.

FIG. 30 is a HSC 7.1 SIM simulation flow sheet illustrating the processing of 50 kg/hr of MoS₂ concentrate feed in a MoS₂—MoO₃-Air looping process with high temperature air production.

FIG. 31 is a HSC 7.1 SIM simulation flow sheet illustrating the processing of 200 kg/hr of MoS₂ concentrate feed in a MoS₂—MoO₃-Air looping process with high temperature air production.

DETAILED DESCRIPTION

Direct Oxidation of MoS₂ with Gaseous O₂

In an embodiment, a method for production of molybdenum(IV) oxide (MoO₂) includes contacting a molybdenite feed with oxygen, wherein an amount of the oxygen is substantially stoichiometric, and oxidizing the molybdenite feed with the oxygen in a furnace to MoO₂.

The term “molybdenite feed” as defined herein refers to molybdenum sulfide (MoS₂) concentrate that primary includes molybdenum disulfide and small amounts of gangue components such as SiO₂, Al₂O₃, FeO, or CaO. The molybdenite feed may include any particulated concentrate composed predominantly of molybdenum disulfide derived from any one of a number of commercial sources. For example, the molybdenite feed may include a concentrate derived from various ore beneficiation processes that are effective to reduce the gangue and other contaminating substances in the concentrate to levels below about 10%. The concentration of the molybdenum disulfide in the ore, as mined, is generally in the order of about 0.03% to about 0.06%, but this concentration may be increased through various beneficiation processes, such as an oil flotation extraction process, to levels of 50% or greater molybdenum, and even of 60% or greater molybdenum.

The oxygen used in the method for production of MoO₂ may include pure oxygen, or a mixture of oxygen and another gas, for example, a mixture of oxygen and nitrogen, air, or oxygen-enriched air. The content of oxygen in air may be about 21%, and the content of oxygen in oxygen-enriched air may be from about 21% to about 100%.

The term “substantially stoichiometric,” as defined herein with regard to the method for production of MoO₂ by oxidation with oxygen but without use of molybdenum(VI) oxide MoO₃ as an oxidant, refers to a ratio of molecular oxygen (O₂) to molybdenite feed (MoS₂) that is 3:1 or about 3:1 (moles O₂:moles MoS₂). The stoichiometric amount is given as a percent of the stoichiometric 3 moles oxidizing agent (molecular oxygen): 1 mole MoS₂ stoichiometry. A stoichiometric percent of 90% to 110% indicates a ratio of moles O₂ to moles MoS₂ of about 2.7:1 to about 3.3:1. The substantially stoichiometric amount may be about 85% to about 115% based on the total amount of molybdenite feed, for example, about 90% to about 110% based on the total amount of molybdenite feed, or about 95% to about 105% based on the total amount of molybdenite feed.

The oxidation of the molybdenite feed with the oxygen may be conducted in a furnace, which for example, can be a flash furnace, a shaft furnace, a multiple hearth furnace, a rotary furnace, a rotary kiln, or a fluid bed furnace.

The oxidation of the molybdenite feed with the oxygen may further be conducted at temperature of about 500° C. to about 1,500° C., for example, 800° C. to about 1,500° C., or 1,100° C. to about 1,500° C.

FIGS. 1 to 10 demonstrate the thermodynamics for the chemical reaction of MoS₂ with gaseous oxygen produced using FactSage software (Bale, C. W., et al. FactSage™ 6.3.1, Thermfact and GTT-Technologies, CRCT, Montreal, Canada (2012)) that model the thermodynamic equilibria of various species under given thermodynamic states. FIGS. 1 to 3 show the predominance phase diagram for the Mo—O₂—SO₂ system at 1,000° C., 1,250° C., and 1,500° C., respectively. These diagrams show that MoO₂, a traditionally difficult compound to isolate during conventional roasting, is stable over a range of operating pressures and temperatures. With increase in temperature, it is observed that MoO₂ becomes the thermodynamically stable species over a more and more narrow O₂ partial pressure. This suggests that an appropriately designed process can operate at or near equilibrium conditions and produce MoO₂ selectively over MoO₃ from MoS₂ concentrates. Additionally, it is apparent from FIGS. 1 to 3 that MoS₂ progresses first to MoO₂ before further oxidation to either molybdenum suboxides or MoO₃. Therefore, an appropriately designed process will take steps to maximize the conversion of MoS₂ to MoO₂ while minimizing any further oxidation. Such steps include promoting the rapid and complete conversion of MoS₂ by using fine particulate MoS₂ feed, high temperature reactor operation, precise MoS₂ and oxygen feed rates and ratios. The molybdenite feed should be free flowing and well dispersed in the oxygen feed to promote complete exposure of the MoS₂ to the oxidizer. Due to the exothermic nature of the reaction between MoS₂ and O₂, it is possible to create a high temperature zone in the furnace wherein the conversion of MoS₂ to MoO₂ takes place. Thus, the term “high temperature zone” as defined herein refers to a portion of a furnace wherein an exothermic reaction (Table 5) between the molybdenum feed and oxygen to produce MoO₂ takes place. The residence time in the high temperature zone can be estimated using Stokes' Law, which relates drag force on a falling particle to the particle's size and the viscosity of the surrounding fluid. Taking into consideration that the largest particle present in the molybdenite feed will fall the fastest, the size of this particle determines the minimum residence time required to perform the desulfurization; all smaller particles will spend a longer time in the high temperature zone. The residence time of the reacting particles in the high temperature zone (1000-1500° C.) will vary from 0.1 to 40 seconds for particle agglomerates on the order of 500 to 1000 μm.

Residence time in high temperature zone of given length, sec Particle size, μm 0.01 m 0.1 m 1.0 m 500 0.39 3.9 39 1000 0.10 0.98 9.8 A flash type reactor is well suited to provide the short residence that ensures complete desulfurization and conversion to MoO₂ without overoxidizing the molybdenum. The term “complete desulfurization” as defined herein means that less than 0.1 weight % of sulfur remains in the molybdenum oxide product(s), for example 0 to less than 0.1 weight %. More preferably, 0 to less than 0.05 weight % of sulfur remains in the molybdenum oxide product(s). Alternative embodiments may include fluid bed reactors. A self-propagating high-temperature synthesis (SHS) technique can be employed (USSR Patent No. 255221). FIG. 4 shows a conventional molybdenite roasting at 400 to 800° C. utilizing a multiple hearth furnace, which exposes the MoS₂ to an excess O₂ environment. It has been shown that by introducing MoS₂ to excess O₂, the MoO₂ formed as an intermediate product is further oxidized in the excess oxygen to MoO₃, thus lowering the yield of MoO₂. The overall chemical reaction for this operation is shown by Equation 1 wherein the x represents the excess O₂ used. MoS₂+(3.5+x)O₂→MoO₃+2 SO₂   Equation 1

When using MoO₃ to produce alloy steels, manufacturers must reduce the oxide to metallic molybdenum. If selective production of MoO₂ were possible, then MoO₂ would be a more desirable material for production of metallic molybdenum than MoO₃ since MoO₂ has higher molybdenum content, and therefore, it requires less reducing agent to produce metallic molybdenum. All prior art attempts to selectively produce MoO₂ from MoS₂ were unsuccessful because the excess amount of O₂ further oxidized MoO₂ to MoO₃. In conventional multiple hearth roasting, excess O₂ is required to achieve complete desulfurization and complete oxidation to MoO₃. In the present disclosure, limiting the amount of oxygen to a stoichiometric amount, selectively produces MoO₂ from MoS₂ without further oxidation of MoO₂ to MoO₃. The appropriate FactSage simulations summarized in Table 1 confirm this result (Bale, C. W., et al. FactSage™ 6.3.1, Thermfact and GTT-Technologies, CRCT, Montreal, Canada (2012)).

TABLE 1 Process Variables in MoS₂ Oxidation with O₂. VARIABLE VALUE Temperature Range 500 to 2,000° C. Moles of MoS₂ 1 Moles of O₂ (in air) 2.85-3.15 % of Stoichiometry 95-105%

Oxidation of MoS₂ with a stoichiometric amount of oxygen is shown by Equation 2. MoS₂+3 O₂ (stoichiometric)→MoO₂+2 SO₂   Equation 2

As can be seen from Equation 2, the maximum amount of MoO₂ produced from the input materials is 1 mole. As seen in FIG. 5, virtually a 100% yield of MoO₂ may be achieved over a wide range of temperatures when operating at equilibrium conditions. While this is promising data, controlling addition of a stoichiometric amount of O₂ would be challenging under plant conditions. Thus, further simulations were performed to understand the reaction under both excess and lean oxygen conditions.

As shown in FIG. 6, when O₂ is present in 5% excess, approximately 30% of the MoO₂ product is converted to gaseous MoO₃ (Mo₃O₉). In effect, 0.7 moles of MoO₂ and 0.3 moles of MoO₃ are produced per mole of MoS₂ oxidized with a 5% excess of O₂. This significantly affects the selectivity of production of MoO₂ and indicates that any amount of excess O₂ may severely reduce the yield of MoO₂.

Under conditions utilizing O₂ in a much lower excess (0.5%), the product distribution is less adversely affected and the selectivity to MoO₂ is much higher (FIG. 7). With a marginal excess of O₂, the S₂ partial pressure is slightly higher than in the case with 5% excess oxygen (FIG. 8). Additionally, greater excess of oxygen leads to higher partial pressures of SO₂ at low temperatures, but lower partial pressures of SO₂ at high temperatures (FIG. 9). From these observations it is apparent that the precise oxygen stoichiometry control to obtain the desired product distribution may not be necessary. When controlling as near to stoichiometric conditions as possible, a shortage of O₂ may be developed, leading to oxygen-lean conditions.

The data indicating adiabatic temperature of varying % O₂ stoichiometry are listed in Table 2. These data demonstrate the feasibility of direct MoO₂ production from MoS₂ using O₂ from the air as an oxidizer. Almost quantitative yields are achieved under proper stoichiometric and thermal control. Table 2 suggests that operating below, at, or even slightly above stoichiometry permits higher yields of MoO₂ with reasonable adiabatic temperatures in 85% nitrogen and 15% oxygen mixture. Additionally, SO₂ present in the off-gas may be captured and used for sulfuric acid production.

TABLE 2 Adiabatic Temperature of Varying % O₂ Stoichiometry. Adiabatic Temperature Adiabatic Moles % O₂ using Yield w/ SO₂ Content Temperature using of O₂ Stoichiometry 15 O₂/85% N₂ (° C.) Air w/ Air, wt. % pure O₂ (° C.) 2.70 90% 1,228 99.9% 19.9% 2,535 2.76 92% 1,236 99.8% 20.3% 2,561 2.82 94% 1,244 99.7% 20.4% 2,588 2.88 96% 1,251 99.6% 20.6% 2,616 2.94 98% 1,258 99.1% 20.8% 2,645 3.00 100% 1,262 96.7% 21.0% 2,674 3.06 102% 1,253 87.2% 20.8% 2,701 3.12 104% 1,241 75.5% 20.4% 2,724 3.18 106% 1,229 63.7% 20.1% 2,742 3.24 108% 1,218 51.8% 19.7% 2,757 3.30 110% 1,207 39.8% 19.5% 2,768 Combined Cycle Oxidation of Mos₂ for the Production of MoO₂

While direct oxidation of MoS₂ with O₂ produces MoO₂ in one step, it is difficult to accurately control the O₂ stoichiometry, so the resulting MoO₂ may be further oxidized to produce MoO₃. This issue can be resolved by introducing MoO₃ as an oxidizing agent, combining direct oxidation and Looping Sulfide Oxidation (“LSO”) simultaneously in a common cycle oxidation process (L. F. McHugh, R. Balliett, J. A. Mozolic, The Sulfide Ore Looping Oxidation Process: An Alternative to Current Roasting and Smelting Practice, JOM, July 2008, 84-87; L. N. Shekhter, C. G. Anderson, D. G. Gribbin, E. Cankaya-Yalcin, J. D. Lessard, L. F. McHugh, Looping Sulfide Oxidation™ Process for Anode Copper Production, Proceedings of the 4^(th) International Symposium on High-Temperature Metallurgical Processing, to be published).

In an embodiment, the looping method for production of molybdenum(IV) oxide may include: oxidation of the molybdenite feed with a mixture comprising MoO₃ and oxygen in a first furnace to MoO₂; removing a portion of MoO₂ from the first furnace; transferring a second portion of MoO₂ from the first furnace to a second furnace; reoxidation of the transferred portion of the MoO₂ in the second furnace to MoO₃; and looping MoO₃ from the second furnace into the first furnace for use as an oxidizing agent.

As shown in FIG. 28, the oxidation of the molybdenum feed takes place in a first furnace (Flash Furnace I), which may be a flash furnace, a shaft furnace, a multiple hearth furnace, a rotary kiln, or a fluid bed furnace. The residence time wherein the reactants are undergoing chemical reactions is longer in the combined cycle operation as compared to the reaction of MoS₂ with only O₂ as outlined above. In the first furnace, MoS₂ contained in the molybdenite feed is converted to MoO₂ in the presence of a MoO₃/preheated air mixture. The oxidation also produces a concentrated SO₂ off-gas stream as a by-product. As used herein, the term “concentrated SO₂ off gas” means the off-gas wherein the content of SO₂ is 20 weight % or greater, and more preferably is 40 weight % or greater. MoO₃ may be particulate MoO₃. A ratio of MoO₃ to oxygen in the oxidizing agent may be from about 1.0:2.5 to about 2.4:1.8, for example from about 1.5:2.0 to about 2.4:1.8 or from about 1.5:2.0 to about 2.0:1.5.

A total amount of the oxidizing agent including MoO₃ and oxygen may be substantially stoichiometric to an amount of the molybdenite feed. The term “substantially stoichiometric” as defined herein with regard to the looping method for production of MoO₂ refers to a ratio of the oxidizing agent [molecular oxygen (O₂) +molybdenum(VI) oxide (MoO₃)] to molybdenite feed (MoS₂) that is [6×(1−a/3)+a]:1 or about [6×(1−a/3)+a]:1 [(moles O₂+moles MoO₃):moles MoS₂] where a represents the moles of O₂ (cf. Equation 4). The stoichiometric amount is given as a percent of the stoichiometric [6×(1−a/3)+a] moles of the oxidizing agent (molecular oxygen+molybdenum (VI) oxide): 1 mole MoS₂ stoichiometry. A stoichiometric percent of 90% to 110% indicates a ratio of moles of the oxidizing agent to moles of MoS₂ of about 0.90×[6×(1−a/3)+a]:1 to about 1.10×[6×(1−a/3)+a]:1. The substantially stoichiometric amount may be about 85% to about 115% based on the total amount of the molybdenum feed, specifically, about 90% to about 110% based on the total amount of the molybdenum feed, more specifically, about 95% to about 105% based on the total amount of the molybdenum feed.

Another benefit of the combined usage of MoO₃ and O₂ for the oxidation of the molybdenite is the reduction of the recycled (re-oxidized) amount of MoO₂ due to the usage of oxygen. When no oxygen is used for the oxidation of MoS₂, more than 85% Mo on molar basis will have to be recycled.

After the oxidation, a portion of MoO₂ may be removed from Flash Furnace I as a product and stored or used as needed. Another portion of MoO₂ may be carried to a second furnace (Flash Furnace II), which may be a flash furnace. In the second furnace, MoO₂ may be converted to MoO₃ by use of an appropriate oxidizing agent, such as oxygen. The oxygen may include pure oxygen, air, or oxygen-enriched air. The stream of the SO₂ off-gas may be carried to the Boiler wherein water steam is generated due to the heat transfer. To facilitate localized condensation of any excess MoO₃ in a given area of the reactor, a portion of the SO₂ off-gas may be recycled to Flash Furnace I. The rest of the SO₂ off-gas may be passed through Catalyst Bed and Heat Exchanger to Acid Absorption Tower for H₂SO₄ (sulfuric acid) production.

The regenerated MoO₃ (for example, condensed particulate MoO₃) may be looped back to the first furnace. The incoming reaction air to the furnace may be preheated to increase the efficiency in the overall system. The off-gas stream from the second flash furnace may be directed to a heat exchanger-boiler system for energy generation and reaction air preheating. Boilers downstream of the second flash furnace system and in the acid plant may be utilized to generate high pressure steam for energy production via turbines. In an embodiment, the oxidation may produce energy in an amount of about 385 to about 400 kiloWatt×hour based on 1,000 kilogram of the molybdenite feed.

As stated above, the presented looping method allows a selective production of MoO₂ without its further oxidation to MoO₃. While not wanting to be bound by a theory, it is understood that oxygen that is present in the oxidizing agent in less than a stoichiometric amount selectively converts some of the molybdenite feed into MoO₂. The rest of the molybdenite is oxidized with MoO₃ to produce MoO₂. Thus, use of the oxidizing agent including both oxygen and MoO₃, allows to obtain a nearly quantitative yield of MoO₂ without any noticeable quantities of MoO₃.

FIGS. 11 to 18 demonstrate the thermodynamics for the chemical reaction of MoS₂ with gaseous oxygen and MoO₃ produced using FactSage software that model the thermodynamic equilibria of various species under given thermodynamic states. As was shown by Equation 2, the stoichiometric amount of oxygen to oxidize 1 mole of MoS₂ to MoO₂ is 3 mole. As follows from Equation 3, the stoichiometric amount of MoO₃ to oxidize 1 mole of MoS₂ to MoO₂ is 6 mole. MoS₂+6 MoO₃→7 MoO₂+2 SO₂   Equation 3

In order to investigate the relationship between the MoO₃ and O₂ as oxidizing agents in combined cycle oxidation, the ratio of MoO₃ to O₂ was varied (Table 3). The reaction stoichiometry for these experiments can be represented by Equation 4, wherein the ratio represents the ratio between MoO₃ and O₂.

$\begin{matrix} \left. {{MoS}_{2} + {a\;{Mo}\; O_{3}} + {\left( {3 - {a/2}} \right)O_{2}}}\rightarrow{{\left( {1 + a} \right){Mo}\; O_{2}} + {2\;{SO}_{2}}} \right. & {{Equation}\mspace{14mu} 4} \end{matrix}$

Under each unique oxidation condition, the equilibrium behavior was noted with attention paid to determining the optimal operating conditions for MoO₂ production.

TABLE 3 Ratios of Oxidizing Agents in the Combined Cycle Production of MoO₂ per mole of MoS₂ (The equilibrium product distributions of each case are given in the indicated figures). Moles of 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 MoO₃ Moles of 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 O₂ Ratio 1:2.5 1:2.0 1:1.64 1:1.38 1:1.17 1:1 1:0.86 1:0.75 Figure 11 12 13 14 15 16 17 18

FIGS. 11 to 18 demonstrate the relationship between the MoO₃: O₂ ratio in the oxidizing composition and the temperature dependence of the production distribution (Table 4). In general, the higher the ratio between the MoO₃ and the O₂ (i.e. the higher the amount of MoO₃ relative to O₂), the higher the temperature at which the MoO₂ begins oxidation to gaseous MoO₃ (Mo₃O₉). This trend agrees with the thermochemical nature of the competing oxidation reactions between MoS₂ and O₂ and MoO₃; oxidation with MoO₃ is less exothermic than oxidation with O₂, so with higher MoO₃ content, the overall equilibrium composition is less affected by elevated temperatures. Lower yields of MoO₂ were observed with a concomitant decrease in the partial pressure of SO₂ and increase in the partial pressure of S₂ suggesting that SO₂ acts as the oxidizer towards MoO₂ during the oxidation of the dioxide to the trioxide. In effect, MoO₂ and SO₂ are not chemically inert towards each other at high temperatures.

TABLE 4 Relationship between Potential Process Performance and O₂/MoO₃ Ratio. Moles O₂ 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 (in air) Moles MoO₃ 1.0 1.2 1.4 1.6 1.2 2.0 2.2 2.4 Adiabatic 1404 1368 1331 1293 1253 1214 1172 1132 Temperature (° C.) Yield 94.6% 95.6% 97.9% 98.7% 99.3% 99.6% 99.8% 99.9% (at Adiabatic Temp) SO₂ Content, 31.7% 33.0% 34.2% 35.4% 36.5% 37.7% 38.9% 40.3% wt. % (at Adiabatic Temp) Optimal 1,100- 1,100- 1,100- 1,100- 1,100- 1,100- 1,100- 1,100- T Range 1,350 1,375 1,375 1,400 1,400 1,400 1,425 1,425 (° C.) [>95% Recovery]

FIGS. 11 to 18 and Table 4 suggest that the combined cycle oxidation of MoS₂ with MoO₃ and O₂ is an effective means to produce MoO₂ with nearly 100% selectivity. Furthermore, it has been determined that the temperature range of this oxidation can be controlled by the ratio of oxidants. These results make it possible the development of a continuous process capable of converting molybdenite feed to the desirable MoO₂. To improve its energy footprint and enable continuous operation, MoO₃ should desirably be produced continuously within the process such that it can be used to oxidize the feed. As stated above, such an operation can be achieved by further oxidation of a portion of the MoO₂ produced during the combined cycle oxidation with O₂ and looping this MoO₃ back to the feed to act as an oxidant (Equation 5). MoO₂+½ O₂→MoO₃ ΔH°=−87.1 kWh   Equation 5

For the combined cycle oxidation of the molybdenite feed in the presence of a mixture of MoO₃ and O₂, a flash reactor can be used to create a high temperature zone in which the conversion of the MoS₂ to MoO₂ takes place. Since the residence time in this high temperature zone will be short, the flash temperature should exceed the boiling point of the looped MoO₃ to ensure that it is fully vaporized, mitigating mass transfer limitations when it reacts with the MoS₂. As previously discussed, the upper temperature of the flash zone is limited by the temperature at which the yield of MoO₂ decreases due to in situ gaseous Mo₃O₉ formation. Additionally, the off-gas produced in the combined cycle oxidation flash reactor is rich in SO₂ (Table 4), and provides another avenue for significant energy capture in a downstream sulfuric acid plant.

The MoO₂ product that is not looped for reoxidation can be collected as a final product. The MoO₂ to be recycled enters a second flash furnace at 600° C. where it is reacted at over 1,100° C. (due to the exothermic nature of the oxidation reaction, Equation 5) in the presence of oxygen in the high temperature zone of the furnace. These conditions lead to the complete oxidation of MoO₂ to MoO₃ (FIG. 19). This gaseous MoO₃ is then cooled in a condensing zone with ambient temperature air to produce MoO₃ in a powder form at 600° C. to be looped to the first flash furnace.

This entire process in the second flash furnace operates free of sulfur (in either the gas or solid phase), so that condensation of sulfuric acid (due to SO₂ or SO₃) in downstream processes is eliminated. As such, energy capture from the MoO₂ reoxidation with O₂ to MoO₃ for looping is maximal. This energy capture is realized as preheating reaction air for this second flash furnace and as high pressure steam generation.

Production of Molybdenum Suboxides During Molybdenite Conversion to Molybdenum Dioxide

FIGS. 20-24 demonstrate the thermodynamic feasibility of producing suboxides of molybdenum from molybdenite under sulfur-oxygen atmospheres. FIGS. 20-24 are predominance diagrams produced using FactSage software that models the thermodynamic equilibria of various species under given thermodynamic states. From a predom diagram it is possible to define the species that will be present when thermodynamic equilibrium is reached at a given temperature and pressure. FIGS. 20-24 describe such equilibria for the Mo—SO₂—O₂ system in the temperature range of 500-1,000° C.

From FIGS. 20-23 it is apparent that the suboxides of molybdenum (Mo₄O₁₁, Mo₈O₂₃, Mo₉O₂₆) are formed under specific SO₂ and O₂ partial pressures over distinct temperature ranges. FIG. 1 demonstrates that by temperatures of ca. 1,000° C., no intermediate suboxides are formed with only MoO₂ in the solid state and Mo₄O₁₂ (gaseous MoO₃) being stable. The partial pressure of O₂ is the key to determining the species of suboxide formed, with the oxygen partial pressure range of each stable species narrowing with increasing temperature (cf. FIGS. 20-23).

It must be noted that the production of intermediate molybdenum suboxides is a process that takes place at low temperatures (relative to the production of MoO₂ described in the LSO process). During this low temperature process, direct production of the suboxides from the molybdenite concentrate is impossible (FIGS. 20-23). Instead, the molybdenum must first pass through a MoO₂ state before further oxidation to one of the several suboxide states. This conversion can be accomplished by first producing MoO₂ from the MoS₂ concentrate and then adding a very slight excess of O₂ to create the necessary oxygen partial pressure to bring about the conversion to a molybdenum suboxide. Again, while the LSO process is capable of producing MoO₂ even in slight excesses of O₂, this process differs in that suboxides are produced when a slight excesses of O₂ is present; this difference is due to the respective temperature ranges of the two processes.

EXAMPLES

Oxidation of Molybdenite with Metal Oxides

To determine the extent to which sulfide minerals are oxidized with metal oxides, a testing was performed. The amount of desulfurization achieved in mixing the sulfide and metal oxide was determined. In one test, MoS₂ was mixed with MoO₃ to achieve 98.5% desulfurization producing MoO₂ as a primary product. These results correlate well with the performed calculations, as can be seen below in FIG. 24 (L. F. McHugh, R. Balliett, J. A. Mozolic, The Sulfide Ore Looping Oxidation Process: An Alternative to Current Roasting and Smelting Practice, JOM, July 2008, 84-87).

Since feeding stoichiometric amounts of two powders is easier than feeding stoichiometric amounts of a powder and a gas, the effect of running in both excess and lean conditions has been investigated (FIGS. 26 and 27).

With 5% excess MoO₃ (FIG. 25), formation of an intermediate solid molybdenum oxide between 500° C. to 900° C. (Mo₄O₁₁) was observed. In contrast, at a temperature above 900° C. and until approximately 1,400° C., a high yield of MoO₂ is observed. Thus, running a reaction with a small excess of MoO₃ still allows complete desulfurization of the molybdenum feed and full conversion of MoS₂ to the desired product (MoO₂).

When operating at a 5% shortage of MoO₃ (FIG. 26), full conversion of MoS₂ is still achieved at a temperature in the range of 1,100° C. to 1,400° C. with high selectivity to MoO₂. This situation is very similar to that wherein the oxidation of MoS₂ is carried out under lean O₂ conditions.

While both of the foregoing reactions yield MoO₂ as the product, they differ substantially from an energy generation perspective (Table 5). The reaction of MoS₂ with O₂ is extremely exothermic, allowing for high energy capture potential. In contrast, the reaction of MoS₂ with MoO₃ is endothermic until approximately 800° C. At or above this temperature, MoO₃ exists as either a molten liquid or a gas and its reaction with MoS₂ is exothermic. Accordingly, it is more desirable to operate at a higher temperature, wherein the kinetics are faster, provided the particles of the reagents are small enough in order to mitigate diffusion limitations. Thus, ΔH_(rxn) is shown for both 25° C. and 1,200° C. in Table 5.

TABLE 5 Comparison of the Heats of Reaction during the Oxidation of Molybdenite with Different Oxidants. MoS₂ + O₂ MoS₂ + 3 O₂ = MoO₂ + 2 SO₂ ΔH° = −251.0 Wh MoS₂ + 3 O₂ = MoO₂ + 2 SO₂ ΔH_(1200° C.) = −249.0 Wh MoS₂ + MoS₂ + 6 MoO₃ = 7 MoO₂ + 2 SO₂ ΔH° = +10.2 Wh MoO₃ MoS₂ + 6 MoO₃ = 7 MoO₂ + 2 SO₂ ΔH_(1200° C.) = −89.8 Wh

Oxidation of MoS₂ with O₂ has a greater potential for energy capture than the oxidation with MoO₃. However, reacting MoS₂ with MoO₃ is a practically desirable reaction, because having a small excess or shortage of MoO₃ does not detrimentally impact the yield of MoO₂. Thus it was determined that oxidation by a combination of MoO₃ and O₂ could be beneficial for the production of MoO₂. The first step in doing so was to determine what the adiabatic temperatures would be for various ratios of MoO₃ to O₂ (Table 4). Calculations were performed using the FactSage software (Bale, C. W., et al. FactSage™ 6.3.1, Thermfact and GTT-Technologies, CRCT, Montreal, Canada (2012)).

Table 4 demonstrates that for this range of reagent ratios, the adiabatic temperature is between 1,111° C. to 1,381° C. In this temperature range, MoO₃ is completely vaporized (FIG. 27). Since MoO₃ is present in a vapor, mixing of the MoS₂ with MoO₃ is much simpler, minimizing the mass transfer limitations to the reaction.

Due to a decrease in yield of MoO₂ with an increase in temperature and to ensure a stable adiabatic temperature, a reagent ratio of 2.2 moles MoO₃:1.9 moles O₂ was chosen for sample calculations. This ratio allows operation at high enough temperature to avoid MoO₃ condensation on the walls of the furnace, but does not affect yield of MoO₂. It should be noted that this reaction proceeds with all stoichiometric combinations of MoO₃ and O₂ but sample calculations were only performed for this particular ratio.

As can be seen in Table 6, this combination of oxidizing agents allows for both low and high temperature exothermic production of MoO₂.

TABLE 6 Oxidation of 1 mole MoS₂ with 2.2 moles MoO₃ and 1.9 moles O₂ at Standard Conditions and 1,200° C. MoO₃/O₂ MoS₂ + 2.2 MoO₃ + 1.9 O₂ = ΔH° = −155.2 Wh Mix 3.2 MoO₂ + 2 SO₂ MoS₂ + 2.2 MoO₃ + 1.9 O₂ = ΔH_(1200° C.) = 3.2 MoO₂ + 2 SO₂ −190.6 Wh Heat and Material Balance Calculations for Configuration Including Flash Furnace

The heat and material balances for each processing step in FIG. 28 were calculated using HSC Chemistry 7.1 software and its SIM 7.1 module (Roine, A., et al. HSC 7.11, Outotec, Pori, Finland (2011)). The heat and material balances were calculated for a 37/63% mixture of MoO₃/O₂ with a starting amount of 1,000 kg of MoS₂ to show energy generated in this example. The results are shown in Tables 7 to 17.

1. Oxidation of Molybdenite

A process which takes place in Flash Furnace I may be represented by Equation 6: MoS₂+2.2 MO₂+1.9 O₂→3.2 MoO₃+2 SO₂   Equation 6 ΔH°=−155 kWh

The ratio of MoO₃:O₂ 37/63% was used in the furnace. The air was introduced at 80° C. which was preheated in the heat exchanger of the acid absorption tower. The adiabatic temperature was 1,170° C. and the products were cooled down to 600° C. with the SO₂ recycle.

TABLE 7 Heat and Material Balance on Flash Furnace I. INPUT SPECIES (1) Temper. Amount Amount Amount Latent H Total H Formula ° C. kmol kg Nm³ kWh kWh Sulfide Feed 25.000 6.248 1000.000 0.198 0.00 −482.46 MoS₂ 25.000 6.248 1000.000 0.198 0.00 −482.46 Oxide Feed 500.000 13.745 1978.408 0.422 161.04 −2681.85 MoO₃ 500.000 13.745 1978.408 0.422 161.04 −2681.85 Air Feed 83.142 56.526 1630.806 1266.961 26.68 26.68 N₂(g) 83.142 44.656 1250.963 1000.899 21.02 21.02 O₂(g) 83.142 11.871 379.843 266.062 5.66 5.66 OUTPUT SPECIES (1) Temper. Amount Amount Amount Latent H Total H Formula ° C. kmol kg Nm³ kWh kWh MoO₂ 1170.934 19.993 2557.817 0.395 496.54 −2768.35 MoO₂ 1170.934 19.993 2557.817 0.395 496.54 −2768.35 Flue Gas 1170.934 57.151 2051.398 1280.964 660.94 −369.28 N₂(g) 1170.934 44.656 1250.963 1000.899 452.28 452.28 SO₂(g) 1170.934 12.495 800.435 280.065 208.66 −821.56 kmol Kg Nm³ kWh kWh BALANCE: 0.625 0.000 13.779 969.75 0.00

TABLE 8 Heat and Material Balance on MoO₂ Product and Recycle Streams. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (2) Formula ° C. kmol kg Nm³ kWh kWh MoO₂ Product (Out) 1170.934 6.248 799.318 0.124 155.17 −865.11 MoO₂ 1170.934 6.248 799.318 0.124 155.17 −865.11 MoO₂ Recycle 1170.934 13.745 1758.499 0.272 341.37 −1903.24 MoO₂ 1170.934 13.745 1758.499 0.272 341.37 −1903.24 Flue Gas 1170.934 57.151 2051.398 1280.964 660.94 −369.28 N₂(g) 1170.934 44.656 1250.963 1000.899 452.28 452.28 SO₂(g) 1170.934 12.495 800.435 280.065 208.66 −821.56 SO₂ Recycle 400.000 309.175 11097.590 6929.720 1071.13 −4502.09 N₂(g) 400.000 241.578 6767.421 5414.633 745.72 745.72 SO₂(g) 400.000 67.597 4330.169 1515.087 325.40 −5247.82 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (2) Formula ° C. kmol kg Nm³ kWh kWh MoO₂ Product (Out) 600.000 6.248 799.318 0.124 70.81 −949.47 MoO₂ 600.000 6.248 799.318 0.124 70.81 −949.47 MoO₂ Recycle 600.000 13.745 1758.499 0.272 155.78 −2088.83 MoO₂ 600.000 13.745 1758.499 0.272 155.78 −2088.83 Flue Gas 600.000 57.151 2051.398 1280.964 312.34 −717.88 N₂(g) 600.000 44.656 1250.963 1000.899 215.39 215.39 SO₂(g) 600.000 12.495 800.435 280.065 96.95 −933.26 SO₂ Recycle 600.000 309.175 11097.590 6929.720 1689.68 −3883.54 N₂(g) 600.000 241.578 6767.421 5414.633 1165.19 1165.19 SO₂(g) 600.000 67.597 4330.169 1515.087 524.49 −5048.73 kmol Kg Nm³ kWh kWh BALANCE: 0.000 0.000 0.000 0.00 0.00

2. Reoxidation of MoO₂ to MoO₃

In Flash Furnace II the reoxidation of MoO₂ to MoO₃ took place (Equation 5). The air in this reaction was preheated to 500° C. and 10% excess air was used. The adiabatic/flash temperature was around 1,115° C. and the products were cooled down to 600° C. with cooling air at 25° C. The product MoO₃ powder was transferred back in to Flash Furnace I to be used as an oxygen source.

TABLE 9 Heat and Material Balance for Flash Furnace II. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (4) Formula ° C. kmol kg Nm³ kWh kWh MoO₂ Recycle 600.000 13.745 1758.499 0.272 155.78 −2088.83 MoO₂ 600.000 13.745 1758.499 0.272 155.78 −2088.83 Reaction Air 503.117 32.726 944.151 733.504 131.42 131.42 N₂(g) 503.117 25.853 724.242 579.468 102.71 102.71 O₂(g) 503.117 6.872 219.909 154.036 28.71 28.71 Excess Air 503.117 3.273 94.415 73.350 13.14 13.14 N₂(g) 503.117 2.585 72.424 57.947 10.27 10.27 O₂(g) 503.117 0.687 21.991 15.404 2.87 2.87 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (4) Formula ° C. kmol kg Nm³ kWh kWh MoO₃ 1114.039 13.745 1978.408 0.422 619.16 −2223.74 MoO₃ 1114.039 13.745 1978.408 0.422 619.16 −2223.74 Flue Gas 1114.039 29.126 818.657 652.818 279.46 279.46 N₂(g) 1114.039 28.439 796.666 637.415 272.49 272.49 O₂(g) 1114.039 0.687 21.991 15.404 6.97 6.97 kmol Kg Nm³ kWh kWh BALANCE: −6.872 0.000 −153.886 598.28 0.00

TABLE 10 Heat and Material Balance for Cooling MoO₃ Product INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (5) Formula ° C. kmol kg Nm³ kWh kWh MoO₃ 1114.039 13.745 1978.408 0.422 619.16 −2223.74 MoO₃ 1114.039 13.745 1978.408 0.422 619.16 −2223.74 Flue Gas 1114.039 29.126 818.657 652.818 279.46 279.46 N₂(g) 1114.039 28.439 796.666 637.415 272.49 272.49 O₂(g) 1114.039 0.687 21.991 15.404 6.97 6.97 Cooling Air 25.000 114.428 3301.289 2564.746 0.00 0.00 N₂(g) 25.000 90.398 2532.361 2026.149 0.00 0.00 O₂(g) 25.000 24.030 768.928 538.597 0.00 0.00 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (5) Formula ° C. kmol kg Nm³ kWh kWh MoO₃ 600.000 13.745 1978.408 0.422 199.63 −2643.26 MoO₃ 600.000 13.745 1978.408 0.422 199.63 −2643.26 Flue Gas 600.000 143.554 4119.945 3217.564 698.98 698.98 N₂(g) 600.000 118.837 3329.027 2663.564 573.18 573.18 O₂(g) 600.000 24.717 790.919 554.000 125.80 125.80 kmol Kg Nm³ kWh kWh BALANCE: 0.000 0.000 0.000 0.00 0.00

TABLE 11 Heat and Material Balance for Boiler 1. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (3) Formula ° C. kmol kg Nm³ kWh kWh Flue Gas 600.000 366.326 13148.988 8210.684 2002.02 −4601.42 N₂(g) 600.000 286.234 8018.384 6415.532 1380.57 1380.57 SO₂(g) 600.000 80.092 5130.603 1795.152 621.45 −5981.99 Water 25.000 52.110 938.775 1.024 0.00 −4134.99 H₂O(100 bar) 25.000 52.110 938.775 1.024 0.00 −4134.99 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (3) Formula ° C. kmol kg Nm³ kWh kWh Flue Gas 400.000 366.326 13148.988 8210.684 1269.13 −5334.31 N₂(g) 400.000 286.234 8018.384 6415.532 883.57 883.57 SO₂(g) 400.000 80.092 5130.603 1795.152 385.56 −6217.88 Steam 350.000 52.110 938.775 1167.977 282.97 −3402.10 H₂O(100 bar) 350.000 52.110 938.775 1167.977 282.97 −3402.10 kmol Kg Nm³ kWh kWh BALANCE: 0.000 0.000 1166.953 −449.92 0.00

TABLE 12 Heat and Material Balance for Catalyst Bed. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (8) Formula ° C. kmol kg Nm³ kWh kWh SO₂ Off-gas 60.000 57.151 2051.398 1280.964 17.59 −1012.63 SO₂(g) 60.000 12.495 800.435 280.065 4.94 −1025.28 N₂(g) 60.000 44.656 1250.963 1000.899 12.65 12.65 Air 25.000 44.626 1287.479 1000.232 0.00 0.00 O₂(g) 25.000 9.371 299.876 210.049 0.00 0.00 N₂(g) 25.000 35.255 987.602 790.183 0.00 0.00 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (8) Formula ° C. kmol kg Nm³ kWh kWh SO₃ for Acid 425.108 95.530 3338.876 2141.163 361.04 −1012.63 Absorption Tower SO₂(g) 425.108 12.495 1000.352 280.065 86.49 −1287.18 N₂(g) 425.108 79.911 2238.565 1791.082 263.76 263.76 O₂(g) 425.108 3.124 99.959 70.016 10.80 10.80 kmol Kg Nm³ kWh kWh BALANCE: −6.248 0.000 −140.032 343.45 0.00

TABLE 13 Heat and Material Balance for Heat Exchanger A. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (9) Formula ° C. kmol kg Nm³ kWh kWh SO₃ for 425.108 95.530 3338.876 2141.163 361.04 −1012.63 Acid Absorption SO₃(g) 425.108 12.495 1000.352 280.065 86.49 −1287.18 N₂(g) 425.108 79.911 2238.565 1791.082 263.76 263.76 O₂(g) 425.108 3.124 99.959 70.016 10.80 10.80 Water 25.000 17.341 312.396 0.341 0.00 −1376.00 H₂O(100 bar) 25.000 17.341 312.396 0.341 0.00 −1376.00 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (9) Formula ° C. kmol kg Nm³ kWh kWh SO₃ for 160.000 95.530 3338.876 2141.163 117.16 −1256.51 Acid Absorption SO₃(g) 160.000 12.495 1000.352 280.065 26.16 −1347.51 N₂(g) 160.000 79.911 2238.565 1791.082 87.50 87.50 O₂(g) 160.000 3.124 99.959 70.016 3.50 3.50 Steam 350.000 17.341 312.396 388.668 94.16 −1132.12 H₂O(100 bar) 350.000 17.341 312.396 388.668 94.16 −1132.12 kmol Kg Nm³ kWh kWh BALANCE: 0.000 0.000 388.327 −149.72 0.00

TABLE 14 Heat and Material Balance for Acid Absorption Tower. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (10) Formula ° C. kmol kg Nm³ kWh kWh SO₃ Feed 160.000 95.530 3338.876 2141.163 117.16 −1256.51 SO₃(g) 160.000 12.495 1000.352 280.065 26.16 −1347.51 N₂(g) 160.000 79.911 2238.565 1791.082 87.50 87.50 O₂(g) 160.000 3.124 99.959 70.016 3.50 3.50 Acid Feed 75.000 12.495 1450.564 0.000 37.77 −3876.11 H₂SO₄*H₂O 75.000 12.495 1450.564 0.000 37.77 −3876.11 Water (Boiler) 50.000 27.675 498.562 0.544 14.47 −2182.79 H₂O(1 bar) 50.000 27.675 498.562 0.544 14.47 −2182.79 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (10) Formula ° C. kmol kg Nm³ kWh kWh Acid 125.000 24.991 2450.916 1.331 102.01 −5548.57 H₂SO₄ 125.000 24.991 2450.916 1.331 102.01 −5548.57 Flue Gas 125.000 83.034 2338.524 1861.098 67.32 67.32 N₂(g) 125.000 79.911 2238.565 1791.082 64.75 64.75 O₂(g) 125.000 3.124 99.959 70.016 2.58 2.58 Steam (Boiler) 125.000 27.675 498.562 620.286 27.60 −1834.17 H₂O(1 bar) 125.000 27.675 498.562 620.286 27.60 −1834.17 kmol Kg Nm³ kWh kWh BALANCE: 0.000 0.000 341.008 27.54 0.00

TABLE 15 Heat and Material Balance for Heat Exchanger B. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (11) Formula ° C. kmol kg Nm³ kWh kWh Steam from AAT 125.000 27.675 498.562 0.544 58.14 −2139.12 H₂O(1 bar) 125.000 27.675 498.562 0.544 58.14 −2139.12 Air 25.000 92.525 2669.372 2073.814 0.00 0.00 N₂(g) 25.000 73.095 2047.629 1638.313 0.00 0.00 O₂(g) 25.000 19.430 621.744 435.501 0.00 0.00 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (11) Formula ° C. kmol kg Nm³ kWh kWh Water 50.000 27.675 498.562 0.544 14.47 −2182.79 H₂O(1 bar) 50.000 27.675 498.562 0.544 14.47 −2182.79 Preheated Air 83.142 92.525 2669.372 2073.814 43.68 43.68 N₂(g) 83.142 73.095 2047.629 1638.313 34.41 34.41 O₂(g) 83.142 19.430 621.744 435.501 9.27 9.27 kmol kg Nm³ kWh kWh BALANCE: 0.000 0.000 0.000 0.00 0.00

TABLE 16 Heat and Material Balance for Heat Exchanger C. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (7) Formula ° C. kmol kg Nm³ kWh kWh Flue Gas 600.000 143.554 4119.945 3217.564 698.98 698.98 N₂(g) 600.000 118.837 3329.027 2663.564 573.18 573.18 O₂(g) 600.000 24.717 790.919 554.000 125.80 125.80 Air 83.142 35.998 1038.566 806.854 16.99 16.99 N₂(g) 83.142 28.439 796.666 637.415 13.39 13.39 O₂(g) 83.142 7.560 241.900 169.439 3.61 3.61 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (7) Formula ° C. kmol kg Nm³ kWh kWh Flue Gas 500.000 143.554 4119.945 3217.564 571.42 571.42 N₂(g) 500.000 118.837 3329.027 2663.564 468.88 468.88 O₂(g) 500.000 24.717 790.919 554.000 102.54 102.54 Preheated Air 503.117 35.998 1038.566 806.854 144.56 144.56 N₂(g) 503.117 28.439 796.666 637.415 112.98 112.98 O₂(g) 503.117 7.560 241.900 169.439 31.58 31.58 kmol kg Nm³ kWh kWh BALANCE: 0.000 0.000 0.000 0.00 0.00

TABLE 17 Heat and Material Balance for Boiler 2. INPUT SPECIES Temper. Amount Amount Amount Latent H Total H (6) Formula ° C. kmol kg Nm³ kWh kWh Flue Gas 500.000 143.554 4119.945 3217.564 571.42 571.42 N₂(g) 500.000 118.837 3329.027 2663.564 468.88 468.88 O₂(g) 500.000 24.717 790.919 554.000 102.54 102.54 Water 25.000 30.247 544.903 0.594 0.00 −2400.12 H₂O(100 bar) 25.000 30.247 544.903 0.594 0.00 −2400.12 OUTPUT SPECIES Temper. Amount Amount Amount Latent H Total H (6) Formula ° C. kmol kg Nm³ kWh kWh Flue Gas 150.000 143.554 4119.945 3217.564 146.02 146.02 N₂(g) 150.000 118.837 3329.027 2663.564 120.44 120.44 O₂(g) 150.000 24.717 790.919 554.000 25.57 25.57 Steam 350.000 30.247 544.903 677.941 164.25 −1974.72 H₂O(100 bar) 350.000 30.247 544.903 677.941 164.25 −1974.72 kmol kg Nm³ kWh kWh BALANCE: 0.000 0.000 677.347 −261.15 0.00

Based on these calculations, an energy flow sheet diagram was prepared (FIG. 29). The energy input required to operate this given starting composition was zero. This starting composition of 37% MoO₃/63% O₂ yields 387 kWh-value of high pressure steam (350° C., 100 bar) per 1,000 kg MoS₂.

The potential for energy capture was evaluated for each of the MoO₃:O₂ ratios investigated above (Table 18). As can be seen, the amount of energy to be captured ranges from 385 to 400 kWh per 1,000 kg MoS₂.

TABLE 18 Energy Capture with Varying Stoichiometric Ratios of MoO₃/O₂ (in Air) in MoO₂ Production (per 1,000 kg MoS₂) Moles of MoO₃ 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 Moles of O₂ 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 (in air) Adiabatic 1404 1368 1331 1293 1253 1214 1172 1132 Temperature (° C.) Energy Value 400 398 396 393 391 389 387 385 (kWh) Heat and Material Balance Calculations for Configuration Including Rotary Kiln

In the configurations presented here, the key process steps have been modeled; these steps are: (1) deoiling and the concentrate and blending of the concentrate and recycled molybdenum trioxide; (2) reaction of the molybdenum disulfide concentrate with molybdenum trioxide to selectively produce molybdenum dioxide in a rotary kiln; (3) splitting of the molybdenum dioxide into the product stream and the stream to be oxidized and recycled; (4) oxidation of the molybdenum dioxide to molybdenum trioxide in a downer furnace; (5) recycling of the molybdenum trioxide to complete the cycle.

This configuration of processing steps and unit operations is one possible configuration, alternative configurations (including, but not limited to, the use of alternative reaction vessels, e.g. multiple hearth roasters, flash furnaces, etc.) are possible.

Heat losses at the reaction steps have been estimated. Additionally, heat exchangers have been used to maximize heat recovery and minimize the requirement for outside heating. In this model, a heat exchanger is modeled as two units—the first unit cools the hot process gas from the inlet temperature to a specified outlet temperature (potentially constrained by a sulfuric acid dew point consideration); during this cooling, HSC calculates the enthalpy change required. The second unit “calls” the enthalpy change from the cooling unit and applies an enthalpy change of equal magnitude and opposite sign to the cooling air it is supplied; an objective function is used to iterate either the outlet temperature of the cooling air with a given flow rate, or its mass flow rate with a given outlet temperature. In this fashion, an iterative solution for the heat balance is calculated. Because the heat exchangers in this process are linked consecutively to maximize heat recovery and minimize the external heating (via natural gas combustion) required in the furnaces, the mass flow rates of the two linked heat exchanger systems (heat exchangers #1 and #2, and heat exchangers #3, #5, and #6) are specified based on the hot air load required by the furnaces they service. As such, in the iterative solutions for each heat exchanger the mass flow rate is specified and the only degree of freedom available for iteration is the outlet temperature at each unit. A heat transfer efficiency of 90% was assumed. The connectivity of the heat exchangers presented is only one possible configuration; alternative, perhaps more efficient, configurations are possible.

In the model presented below, a deoiler is used to remove water and flotation oil associated with the concentrate before it is fed to the rotary kiln. A blender then adequately mixes the deoiled and dried concentrate with the recycle stream of molybdenum trioxide.

A direct fired rotary kiln is used to perform the looping sulfide oxidation reaction. This rotary kiln has been modeled as two discrete units, though in reality it would function as a direct, countercurrent fired rotary kiln. By modeling the reactor in two discrete steps, the “hockey stick” temperature curve can be better approximated. In the first discrete unit the reaction is carried out to approximately 90% completion and 650° C., in the second discrete unit the reaction is completed at 700° C. This configuration provides a better indication of the natural gas usage and external heating required.

In this case, the amount of hot air required is dependent on the stoichiometry of the reactions taking place in the rotary kiln. As previously discussed, the looping sulfide oxidation reaction provides for a range of molybdenum trioxide to oxygen ratios; in this simulation a ratio of 80% stoichiometry for molybdenum trioxide and 20% stoichiometry for oxygen has been used. Additionally, the requisite amount of air for natural gas combustion has been included. The product gases from the rotary kiln are passed through a heat exchanger and sent for gas cleaning; due to the rich SO₂ content in this gas stream the gas must be kept above the acid dew point. The solid products, now mostly molybdenum dioxide, per the looping sulfide oxidation reaction scheme, are further cooled and split based on the reaction stoichiometry. The fraction to be collected as product is cooled further; the fraction to be recycled into molybdenum trioxide is kept at elevated temperature and sent for processing in the downer furnace.

The downer furnace is the reactor in which the molybdenum dioxide is oxidized to molybdenum trioxide with excess air. In this simulation, 300% excess air is used. The air, along with the air required for natural gas combustion is preheated to elevated temperatures by heat exchangers to minimize the amount of natural gas that must be combusted. The downer furnace is designed to operate at 650° C. to minimize molybdenum trioxide volatilization. A heat loss unit is included in this simulation to model the rapid cooling that takes place in the lower sections of the downer furnace as the converted molybdenum trioxide rapidly cools as it falls the length of the reactor. The gases exiting the reactor are cooled and sent to gas handling. The solids are cooled in a heat exchanger and looped back to the blender to complete the reaction cycle.

To demonstrate the relative amounts of reagents consumed in this process, a range of operating throughputs is presented below. In the first case, a molybdenum concentrate feed containing 50 kg per hour of molybdenum disulfide is considered. This throughput is equivalent to approximately 30,000 lbs molybdenum per year of production. In the second case, 200 kg per hour of molybdenum disulfide is considered, which is equivalent to 120,000 lbs molybdenum per year of production.

FIGS. 30 and 31 show process flow sheet and heat and material balances for the production of MoO₂ at the feed rates of 50 and 200 kg/hr MoS₂ contained, respectively. The heat and material balances for the foregoing processes are summarized in Tables 19A-19B and 20A-20B, respectively.

An alternative configuration not shown here, but that would differ only slightly, is a rotary kiln that is indirectly fired. In this scheme, the rotary kiln would have a firebox, in which natural gas is burned to heat the contents of the kiln via conduction. The natural gas consumption would be slightly higher than that in the directly fired scheme because of the heat losses and inefficiencies associated with heat transfer through the kiln walls. However, the volume of kiln gases requiring treatment in the SO₂ handling system would be smaller.

TABLE 19A Material Balance for 200 kg/hr MoS₂ Concentrate Feed to Rotary Kiln Process To Gas MoS₂ + Hot Air Natural Gas Hot Air Natural Gas Kiln Kiln MoS₂ Handling MoO₃ (Kiln (Kiln (Kiln (Kiln Gases Products Concentrate #1 Feed Low T) Low T) High T) High T) (Hot) (700) Mass Flow, 59 5 297 51 1 4 0 91 263 kg/h Temperature, 25 300 250 414 25 414 25 700 700 C. Pressure, bar 1 1 1 1 1 1 1 1 1 O₂(g), kg/h 0.00 0.00 0.00 11.87 0.00 1.01 0.00 0.00 0.00 N₂(g), kg/h 0.00 1.58 0.00 39.04 0.00 3.31 0.00 42.35 0.00 CO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4.73 0.00 H₂O(g), kg/h 0.00 2.22 0.00 0.00 0.00 0.00 0.00 3.87 0.00 SO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 40.02 0.00 C₉H₂₀ 0.00 1.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00 (NONg), kg/h CH₄(g), kg/h 0.00 0.00 0.00 0.00 1.47 0.00 0.26 0.00 0.00 H₂O(I), kg/h 2.22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C₉H₂₀(NONI), 1.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h MoS₂, kg/h 50.00 0.00 50.00 0.00 0.00 0.00 0.00 0.00 0.00 SiO₂, kg/h 5.56 0.00 32.15 0.00 0.00 0.00 0.00 0.00 32.15 MoO₂, kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 231.80 MoO₃, kg/h 0.00 0.00 215.21 0.00 0.00 0.00 0.00 0.00 0.00 Enthalpy, −58.31 −8.37 −457.87 5.72 −1.90 0.49 −0.33 −60.79 −400.23 kWh

TABLE 19B Material Balance for 50 kg/hr MoS₂ Concentrate Feed to Rotary Kiln Process MoO₂ Hot Air Downer Downer Product MoO₂ Natural (N.G. Hot Air Hot Air Gases Solids MoO₃ (200) Recycle Gas Combustion) (Reaction) (Excess) (Cool) (450) Recycle Mass Flow, 46 218 12 211 103 825 1127 242 242 kg/h Temperature, 200 400 25 198 198 198 350 450 250 C. Pressure, bar 1 1 1 1 1 1 1 1 1 O₂(g), kg/h 0.00 0.00 0.00 49.24 23.97 71.90 72.03 0.00 0.00 N₂(g), kg/h 0.00 0.00 0.00 161.99 78.85 752.60 993.45 0.00 0.00 CO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 33.77 0.00 0.00 H₂O(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 27.65 0.00 0.00 SO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C₉H₂₀(NONg), 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h CH₄(g), kg/h 0.00 0.00 12.31 0.00 0.00 0.00 0.00 0.00 0.00 H₂O(I), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C₉H₂₀(NONI), 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h MoS₂, kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 SiO₂, kg/h 5.56 26.59 0.00 0.00 0.00 0.00 0.00 26.59 26.59 MoO₂, kg/h 40.06 191.74 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MoO₃, kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 215.21 215.21 Enthalpy, −73.33 −343.45 −15.90 10.34 5.03 40.98 −78.39 −402.66 −412.00 kWh

TABLE 20A Material Balance for 200 kg/hr MoS₂ Concentrate Feed to Rotary Kiln Process Natural Natural To Gas MoS₂ + Hot Air Gas Hot Air Gas Kiln Kiln MoS₂ Handling MoO₃ (Kiln (Kiln (Kiln (Kiln Gases Products Concentrate #1 Feed Low T) Low T) High T) High T) (Hot) (700) Mass Flow, 238 22 1189 173 4 13 1 327 1053 kg/h Temperature, 25 300 250 460 25 460 25 700 700 C. Pressure, bar 1 1 1 1 1 1 1 1 1 O₂(g), kg/h 0.00 0.00 0.00 40.28 0.00 3.06 0.00 0.01 0.00 N₂(g), kg/h 0.00 6.38 0.00 132.51 0.00 10.05 0.00 142.56 0.00 CO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 13.30 0.00 H₂O(g), kg/h 0.00 8.89 0.00 0.00 0.00 0.00 0.00 10.89 0.00 SO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 160.09 0.00 C₉H₂₀(NONg), 0.00 6.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h CH₄(g), kg/h 0.00 0.00 0.00 0.00 4.07 0.00 0.77 0.00 0.00 H₂O(I), kg/h 8.89 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C₉H₂₀(NONI), 6.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h MoS₂, kg/h 200.00 0.00 200.00 0.00 0.00 0.00 0.00 0.00 0.00 SiO₂, kg/h 22.22 0.00 128.59 0.00 0.00 0.00 0.00 0.00 128.59 MoO₂, kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 927.21 MoO₃, kg/h 0.00 0.00 860.86 0.00 0.00 0.00 0.00 0.00 0.00 Enthalpy, −233.22 −33.49 −1831.47 21.80 −5.26 1.65 −1.00 −220.49 −1600.91 kWh

TABLE 20B Material Balance for 200 kg/hr MoS₂ Concentrate Feed to Rotary Kiln Process MoO₂ Hot Air Downer Downer Product MoO₂ Natural (N.G. Hot Air Hot Air Gases Solids MoO₃ (200) Recycle Gas Combustion) (Reaction) (Excess) (Cool) (450) Recycle Mass Flow, 182 871 6 108 411 1040 1470 967 967 kg/h Temperature, 200 400 25 144 144 144 350 450 250 C. Pressure, bar 1 1 1 1 1 1 1 1 1 O₂(g), kg/h 0.00 0.00 0.00 25.27 95.87 287.61 287.64 0.00 0.00 N₂(g), kg/h 0.00 0.00 0.00 83.13 315.42 752.60 1151.15 0.00 0.00 CO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 17.33 0.00 0.00 H₂O(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 14.19 0.00 0.00 SO₂(g), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C₉H₂₀(NONg), 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h CH₄(g), kg/h 0.00 0.00 6.32 0.00 0.00 0.00 0.00 0.00 0.00 H₂O(I), kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C₉H₂₀(NONI), 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 kg/h MoS₂, kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 SiO₂, kg/h 22.22 106.36 0.00 0.00 0.00 0.00 0.00 106.36 106.36 MoO₂, kg/h 160.24 766.97 0.00 0.00 0.00 0.00 0.00 0.00 0.00 MoO₃, kg/h 0.00 0.00 0.00 0.00 0.00 0.00 0.00 860.86 860.86 Enthalpy, −293.31 −1373.78 −8.16 3.63 13.77 34.67 42.52 −1610.62 −1648.01 kWh

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. The terms “a” and “an” and “the” herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or.” All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt. %, or, more specifically, 5 wt. % to 20 wt. %”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt. % to 25 wt. %,” etc.). “Combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, herein do not denote any order, quantity, or importance, but rather are used to denote one element from another. Reference throughout the specification to “one embodiment”, “another embodiment”, “an embodiment”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

The terms first, second, third etc. can be used herein to describe various elements, components, regions, layers and/or sections, but these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents. 

What is claimed is:
 1. A looping method for production of molybdenum(IV) oxide, the method comprising: (a) reacting a molybdenite feed with a stoichiometric mixture comprising molybdenum(VI) oxide and oxygen in a first furnace to produce molybdenum(IV) oxide and sulfur(IV) oxide in accordance with a reaction defined by Equation 4: MoS₂ +aMoO₃+(3-a/2)O₂=(1+a)MoO₂+2SO₂  Equation 4, wherein a is the number of moles of MoO₃ per mole of MoS₂, and wherein an amount of aMoO₃+(3-a/2)O₂ in Equation 4 is about 85% to about 115% per mole of MoS₂; (b) removing a first portion of the molybdenum(IV) oxide from the first furnace; (c) transferring a second portion of the molybdenum(IV) oxide from the first furnace to a second furnace; (d) reoxidizing the second portion of the molybdenum(IV) oxide in the second furnace to molybdenum(VI) oxide; and (e) looping the molybdenum(VI) oxide from the second furnace to the first furnace for use as an oxidizing agent.
 2. The looping method for production of molybdenum(IV) oxide of claim 1, wherein a rate of the transferring of the second portion of the molybdenum(IV) oxide to the second furnace is stoichiometrically equivalent to a rate of a molybdenum(VI) oxide usage in the first furnace.
 3. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the oxygen comprises pure oxygen, air, or oxygen-enriched air.
 4. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the oxidation is carried out at a temperature of less than about 1,000° C.
 5. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the oxidation is carried out at a temperature of about 1,300° C. to about 1,400° C.
 6. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the reoxidation is carried out at a temperature of less than about 1,300° C.
 7. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the first furnace is a flash furnace, a shaft furnace, a multiple hearth furnace, a rotary kiln, or a fluid bed furnace.
 8. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the second furnace is a flash furnace, a shaft furnace, a multiple hearth furnace, a rotary kiln, or a fluid bed furnace.
 9. The looping method for production of molybdenum(IV) oxide of claim 8, wherein the flash furnace operates free of sulfur.
 10. The looping method for production of molybdenum(IV) oxide of claim 1, wherein a ratio of molybdenum(VI) oxide to oxygen is calculated according to the formula 6×(1−a/3):a wherein a is equal to the moles of oxygen per 1 mole of molybdenum(IV) sulfide and used to specify an amount of molybdenum (VI) oxide and oxygen used to produce molybdenum(IV) oxide according to Equation
 4. 11. The looping method for production of molybdenum(IV) oxide of claim 1, wherein a ratio of molybdenum(VI) oxide to oxygen is from about 1.0:2.5 to about 2.4:1.8.
 12. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the amount of aMoO₃+(3−a/2)O₂ in Equation 4 is about 90% to about 110% per mole of MoS₂.
 13. The looping method for production of molybdenum(IV) oxide of claim 1, further comprising removing a sulfur(IV) oxide off-gas produced in the oxidation.
 14. The looping method for production of molybdenum(IV) oxide of claim 13, wherein the sulfur(IV) oxide off gas is concentrated.
 15. The looping method for production of molybdenum(IV) oxide of claim 1, wherein a portion of a sulfur dioxide off-gas produced in the oxidation is recycled to the first furnace.
 16. The looping method for production of molybdenum(IV) oxide of claim 1, wherein the oxidation produces energy in an amount of about 385 to about 400 kiloWatt×hour based on 1,000 kilogram of the molybdenite feed. 